Process for hydrogenating edible oils



Patented Sept. 5, 1944 PROCESS FOR HYDROGENATING EDIBLE OILS William J.Paterson, Newton Highlands, Mass.,

assignor to Lever Brothers Company, 'Cambridge, Mass, a corporation ofMaine No Drawing. Application April 2, 1941,

"Serial No. 386,455

19 Claims.

The present invention relates to the preparation of improved productsfrom glyceride oils which are susceptible to an improvement in stabilityagainst rancidity and color or odor, or both. More particularly, theinvention relates to a novel treatment of glyceride oils with hydrogenin the presence of a catalyst to provide an improved product withrespect to color, odor, plasticity, and stability.

The crude oils which are made available to the manufacturer of glyceride,oil products and which have been prepared in accordance with the usualpractice are generally dark in color and contain a substantial amount ofundesirable impurities; such as free fatty acids, gums, mucilaginousmaterial, and the like. Moreover, these oils are normally odoriferousand otherwise objectionable, particularly when the object is to use themas edible substances, for example, for culinary purposes. I

Heretofore, the crude oil generally has been subjected to a series, ofrefining, decolorizing, hydrogenating and deodorizin operations toremove objectionable constituents from the oil and to improve itsstability, color, odor and flavor. The particular procedure followed andthe severity of the treatment depends to a large extent I upon the typeand initial purity of the crude oil as well as the desiredcharacteristics of the final product.

In general, the initial refining of the oil is accomplished bysubjecting the oil to a treatment with caustic alkali, which neutralizesand precipitates the free fatty acids as soaps. At the same time, asubstantial proportion of the gums,

mucilaginous materials, and coloring matter is coagulated and removedalong with .the fatty acid soaps.

To provide an oil of particularly good quality, it is not uncommon tosubject the oil to a rerefining operation in which the refined oil isagain subjected to the action of caustic alkali, generally in a moredilute solution. A further removal of foots, although smaller in amount,is thus effected which is highly beneficial in improving the quality ofthe finished product with respect to color and free fatty acid content.An inherent I disadvantage of the re-refining operation is a substantialfurther loss of neutral oil by saponification and entrainment. andtherefore the use of the re-refining operation is undesirable from aneconomical standpoint.

Further, in accordance with the art of preparing glyceride oil products,the refined oil is bleaching treatment with a usual bleaching agent ofthe carbon or earth type. The bleach ng agents, it is believed, eifect adecolorizing action by absorbing coloring matter from the oil. Thebleaching agents and the absorbed coloring matter are then removed fromthe oil by filtration.

It has been observed that bleaching agents also such as nickel andgenerally at elevated tempera-.

tures. Incidental to the hardening of the oil,

a further improvement in color generally takeslace.

p During such hydrogenation processes the esters of the unsaturatedfatty acid components present in the oils are changed to the esters ofcorresponding saturated fatty acids. The consistency of the materialprogressively approaches that desired as hydrogenation is prolonged. Ifa plastic shortening is desired, it is essential that the moreunsaturated glycerldes be saturated to a degree suflicient to decreasethe fluidity of the oils and sufl'icient to improve the keepingqualities of the unsaturated components.

It is generally recognized that the instablity of glyceride oils is aresult of the tendency of these oils to add on oxygen from theatmosphere at the points of unsaturation in their fatty acid components.It is understood, however, that complete saturation, characterized bythe formation of a hard, brittle solid, is undesirable for most uses. Ingeneral, it is customary to hydro-. genate the oil, for example, avegetable oil to be used in shortenings, to a degree which gives aproduct of substantially lard-like consistency at room temperatures.

The refined and bleached oil, either hydrogenated or unhardened, maythen be deodorized by subjecting the oil to a treatment with steam underreduced pressure conditions.

It is an object or my invention to avoid the multiplicity of processingsteps heretofore regarded as essential in the manufacture of good gradeproducts from glyceride oils. I r

In particular, it is possible by the practice of my invention todispense with the uneconomical nerally improved in color by a subsequentsteps of re-reflning with alkali and decolorizing I such as distillationI edible oil products.

A particular object of my invention is to provide a method wherebyunbleached oils may be bleached and hardened simultaneously tov at leastthe degree required in the production of good grade glyceride oilproducts.

It is another object of my invention to provide a method of hardening'glyceride oils and fats whereby the oils exhibit a greater stabilityagainst oxidation and the development of rancidity as compared with oilshardened to the same iodine value or consistency in accordance with theprior art practice.

Another object of my invention is to provide a method of simultaneouslydecolor-izing and hardening edible oils whereby a product of improvedcolor and odor having desirable plasticity charac teristics may beproduced with a substantial saving in the time and amount of catalystrequired.

The treatment of a prime cottonseed oil for the manufacture of edibleoil products by the methods described above may be taken as typical andinvolves the problem of color removal. "A representative crudecottonseed oil ranges from dark reddish-brown to almost black in colorwhen expressed from the seed. Upon being reflned'with alkali, arepresentative oil exhibits a color of approximately 5.0 red/35.0yellow. All color values referred to herein are in Lovibondunits andhave beenmeasured with a Lovibond tintometer provided with a 5% inchcolumn. A subsequent bleach in accordance with the standard procedureapproved by the American Oil Chemists Society using 6% of the officialiullers earth and employing a temperature of 105-120 C. improves thecolor to approximately 2.0 red/20.0 yellow. Upon hydrogenation toshortening consistency. such an oil usually exhibits a color of 1.0 red/10.0 yellow.

A cottonseed oil which has been re-refined with alkali in addition tobeing subjected to the treatment outlined above, may sometimes, whenchoice oils are used, exhibit after bleaching a color of 1.5 red/ 5.0yellow and after hydrogenation a color of 0.7 red/7.0 yellow. Withrespect to edible cottonseed oil, a color reduction below approximately0.5 red previously has not been believed to be economically orpractically possible by the prior methods of the industry even when thehighest grade raw oil is treated.

Hydrogenated cottonseed oil is utilized principally as the majoringredient of shortening products. In this connection, it is to beobserved that most commercial shortenings average about 2.0 red/20.0yellow and seldom are below 1.5

red/15.0 yellow.

It is known in the art that special methods, and heat treatment of hightemperature, will effect a high degree of color reduction in oils, butthese methods, as a rule, are too severe as well as complex andexpensive for general use, especially in the preparation of Therefore,it is an object of my invention to provide a methodior simultaneouslyhardening products made therewith.

and decolorizlng glyceride oils to eflect a greater improvement in colorthan has been possible heretofore without adversely affecting thedesirable characteristics of the oil with respect to its use,

- for example, for edible purposes.

A particular object of my invention is to provide a method forsimultaneously hardening and decolorizing cottonseed oil to form aplastic edible product which is characterized by an improved water-whiteappearance.

The problem of odor reversion in edible oils may be easily appreciatedby a reference, for ex ample, to soybean oil. The characteristics ofsoybean oil in this connection are discussed in some detail in theEpstein, et al. Patent No. 2,l40,-'

794, issued December 20, 1938.

It is well known that soybean oil refined by prior methods and evenafter the usual hydrogenation to a lard-like consistency, undergoes atype of spoilage which is characterized as reversion, particularly whenexposed to light and air and temperature conditions, such as 385 F.,usually encountered when the shortening is used for deep frying. Thereversion of soybean 'oil is characterized by the development of variousoil? flavors and odors known as a beany" flavor or odor and sometimesdescribed as fishy, which subsequently often become altered with the production of other undesirable flavors and odors, classified as oleo andgrassy.

One of the main objections to the use, for example, of hydrogenatedsoybean oil in shortenings is the reversion to a characteristic butundesirable odor of the oil at the elevated temperatures employed fordeep-frying. In the commercial practice of deep-frying, the fat may bemaintained at a temperature of about 385 F. for several days, any lossfrom the fat body being replaced by additions of further shortening. Theobjectionable odors and flavors which develop are not only undesirableduring frying but also unfavorably affect the odor and flavor of thefood The readily available supply of soybean oil makes its utilizationattractive to the manufacturer. Nevertheless, the use of soybean oil hasbeen greatly limited, particularly in high grade edible products,inasmuch as it has been impossible'to avoid the undesirablecharacteristics of soybean oil, particularly with respect to deepfrying,unless the oil is hydrogenated to the relatively high-titre of 51 C.which corresponds to an iodine value of about 50, and consequentlyhardened to such an extent that it can be used only in restrictedamounts. In general, an iodine value in the range of '70 to and apenetration of 220 to 250 is desired in a hardened soybean oil when theobject is to utilize the oil in shortenings. Even with the use of themost eiiective hydrogenation methods of the prior art, a sat isfactoryshortening capable of meeting the high present-day commercial standardscannot be prepared having more than about 10% to 15% of hydrogenatedsoybean oil.

A particular object of my invention is to provide a method ofsimultaneously hardening and decolorizing glyceride oils such as soybeanoil which imparts stability against reversion and good deep-frycharacteristics to the oils at a desired plasticity whereby the same maybe used 11:11 unlimited amounts, for example, in-shorten- ES. Inaccordance with my invention, I utilize a combination of catalystscomprising a metallic hydrogenating catalyst or its readily reducibleminor sub-groups of groups V and VI, of the periodic classification. 0,of course, represents oxygen; that is, the metals are in the form ofoxides. The minor sub-groups of groups I, II, V and VI of the periodicclassification comprise divisions of the main groups as shown, forexample, in the periodic chart appearing at page 46 of volume I ofInternational Critical Tables. The minor sub-group of group I comprisescopper, silver and gold. The minor sub-group of group II compriseszinc,'cadmium and mercury. The minor sub-group of, group V comprisesvanadium, columbium, tantalum and protoactinium. The minor sub-group ofgroup VI comprises chromium, molybdenum, tungsten and uranium.

It will be apparent that a great number of combinations or mixtures. ofcombinations of the above designated metals are possible in accordancewith my invention. It is to be expected that the activities of theseveral species of catalysts will vary over a wide range and,accordingly, I have selected those metals from' the groups designatedabove which, in general, ex

hibit the greatest activity under the preferred copper-tungsten-oxide,copper uranium oxide and copper-vanadium-oxide.

The proportion of metals indicated by X and Y is not regarded ascritical and may be varied under which the same is to be used, Ingeneral, a substantially atomic ratio of X and Y is preferred foreffecting desirable results in accoijdance with our invention.

over a wide range depending upon the particular; metals selected and theconditions of operation) In general, it is preferred to stabilize theccftalyst by the presence of an alkaline earth metal oxide, such asbarium oxide or calcium oxide,-

although this is not essential. Substantially an atomic ratio of X and Yand of a -mole of alkaline earth metal has generally been found to p bepreferable, but the proportions may be varied as desired and dependingupon the particular metals selected as wellas upon the conditions underwhich the same is to be used.

The exact form of the metals ,or the oxygen in the catalyst is difficultto determine, and it is not intended that my invention shall be limitedto any particular chemical or physical combination. It is possible thatthe catalyst may be a simple mixture of the separate oxides of the twometals present in the catalyst, but it is equally possible that the twometals and the oxygen may be combined to form a distinct and separatechemical compound. It is intended that the scope ofmy invention shallinclude-the use of two or more metals of the type described incombination with oxygen, regardless of the exact chemical or physicalstructure of the composition. It is possible that even as to those oxidecatalysts which, at the present time, do not appear to have a preferredactivity, a modification may be made in their physical form or struc-'ture which may make their use desirable.

Any of a number of varied methods may be employed in preparing the oxideportion of the catalyst, the simplest of which is possibly a directcombination produced by grinding together amixture of the selectedoxidesand subsequently heating the mixture to an elevated temperature.Improved results are obtained by precipitating a mixed salt from asolution of coppernitrate and calcium nitrate by the addition thereto ofa solution containing ammonium dichromate and ammonium hydroxide. Theprecipitate is dried,

pulverized, and decomposed at an elevated temperature to produce a blackoxide mass.

A more-active catalyst as wellas one more uniform and capable of givingreproducible results, may be made by precipitating mixed carbonate froma solution containing the desired proportions of chromium nitrate,copper nitrate,

and barium nitrate by the addition thereto of a solution containingammonium carbonate. The precipitate is washed, dried, pulverized, anddecomposed at approximately 350 C.

The metallic hydrogenating catalyst which I prefer to use is nickel,although satisfactory results may be obtained with cobalt and, to alesser degree, with platinum and palladium. It is intended that myinvention shall include the use Of compounds of the above metals whichare readily reducible during hydrogenation to form the metallichydrogenating catalyst.

'.For convenience, the invention will be described more particularly byreference to the preferred use of active nickel. In general, the.conditions of operation efiective when active nickel is used willobtain for the other species except that a relatively larger proportionof such other species may be required for efiecting equivalent results.

The nickel component of the catalyst may be prepared in any convenientmanner, for example, as set forth in the patent to Paterson, No.2,123,342, issued July 12, 1938. A preferred method comprises thetreatment of electrolytically precipitated nickel hydroxide which may beprepared by passing direct current through a cell using nickel as theanode and using a dilute solution of an alkali salt of a weak acid as anelectrolyte. The nickel hydroxide so .preparedmay be reduced by means ofpure hydrogen gas at a temperature of from 300 C. to 500 C.

The catalyst may be prepared by adding the nickel component to themetallic oxide component in suitable proportions.

However, for convenience, the components are separately added to the oil'to be treated. The amount of the oxide component is preferablyapproximately .2 per cent based on the weight of the oil, while thenickel component is preferably approximately .001 per cent. It is to beunderstood that other proportions may be used in accordance with myinvention, as will be discussed more fully hereinafter.

Oxide catalysts, of the kind disclosed above, have been used heretoforein the hydrogenation of various organic. compounds to produce alcohols,hydrocarbons, and similar unsaponifiable matter. In particular, inaccordance with the prior art, the hydrogenation of glyceride oils usingan oxide catalyst would result in the formation of unsaponifiable mattercomprising higher ketones, such as palmitone and stearone;

matter.

Accordingly, in addition to providing for the simultaneous hardening anddecolorizing of glyceride oils to effect an improvement in color andstability, having the advantages and ramifications discussed above, myinvention further provides an operation durin the hydrobleaching processto effectively retard the formation of unsaponifiable matter. By myprocess, a decolorized and hardened product suitable after filtering,deodorizing, 'texturizing, and like finishing operations, for use as ashortening is obtainable. In addition as to oils, such as, for example,soybean oil, a product is obtained which is stable against reversion.These products hav unsaponifiable components but only in amountscomparable with that ordinarily present in good grade commercialshortenings. In fact, with my process, uniform products may be made withless than 1.0% unsaponifiable components.

It is an object of my invention to provide a method of using oxidecatalysts in combination with metallic hydrogenating catalysts in whichthe formation of unsaponifiable matter is effectively retarded.

, I am aware that the use of metals, such as nickel as a catalyst in thehydrogenation of glyceride oils at elevated temperatures is well knownin the art. The present invention relates to the discovery that thehardening of vegetable oils by the use of hydrogen gas may be moreeffectively accomplished by the simultaneous use of an active metal andmetal oxide catalyst of the type described above, than is to be expectedif the re,- sults obtained using theactive metal and the metal oxidetype of catalyst, respectively, on separate samples, are added.

In other words, an unexpected synergistic action results in thesimultaneous use of the metal catalyst and metal oxide catalystdescribed above, which permits the simultaneous decoloriza' ion,

stabil zation, and hardening of glyceride oils to produce products ofimproved characteristics and with a material saving in processing.

For convenience, the process is described in the specific examples as abatch operation, as by so doing-. simple and easily understood standardequipment may be used. However, it will be apparent. that the processmay be carried outina continuous manner.

For example, the oil may be heated and maintained in contactwithhydrogen for a desired period of time in an elongated restrictedpassageway through which' the oil may be passed continuously orsemi-continu-' erence is had to the following table of test resultsobtained with a representative refined prime cottonseed oil having acolor of 14.7 red and 35 yellow and a standard bleach of 1.7 red/17yellow, and an iodine value of 108.

Table I Catalyst I. V. No. Temp. Time Percent (6st) Cu-Cr-O asses:

Referring to the Table I, test No. 1, using ".5%

of CuCr--O catalyst yielded excellent color and adequate hydrogenation,but because of the relatively high amount of catalyst used, as well asthe time required (sixty minutes), the unsaponiflable matter in the oilincreased to 1.16%. In test No. 2-, with a reduction of oxide catalystto .2%, and with a reduction in time to thirty minutes, the final colorobtained was the equivalent of test No. 1, but the amount ofhydrogenation was unsatisfactory. -In tests Nos. 3 and 4, in which theoxide catalyst contained .01% and .005% metallic nickel respectively,the oil became unduly hard before a sufficient temperature could bereached to obtain the best color removal. Test No. 5, using a preferredcatalyst combination, gave sufficient hydrogenation in fifteen minuteswith a satisfactory color reduction to .2 red/2 yellow. Test No. 6,showing the use of a nickel catalyst alone, indicates that for smallamounts in the neighborhood of .001%, hydrogenation of the oil isnegligible and color reduction is poor- By comparing the resultsobtained in test No. 5, using both nickel and oxide catalyst, with theresults obtained in tests'Nos. 2 and 6, using the same amount of oxideor nickel catalyst alone, it will be apparent that a very pronouncedsynergistic eflect takes place .Whichwould not be expected from theresults obtained with the oxide or nickel catalyst alone.

For more desirable results, it is preferred to carry out the inventionat relatively high pressures in the neighborhood of 100 atmospheres ormore, as set forth in Table I above. It is to be understood, however,that the pressure conditions are not critical and that desirabl resultsmay also be obtained at pressures as low as atmospheric, although thisrequires the use of an increased amount of metallic nickel to obtainadequate hydrogenation.

The following is a table of test results at atmospheric pressuresobtained with the prime cottonseed oil used in the experments at highpressures given above:

Table II Catalyst 0 Percent Percent Cu-Gr-O Ni Color onocamww ammon a-nIn a period of sixty minutes, at atmospheric pressure, test No. 1 with0.2% copper-chromiumoxide alone gave fair color but no hydrogenation andtest No. 3 with 0.01% nickel alone gave poor hydrogenation and poorcolor. By reason of the synergistic effect described above, test No. 2with identical amounts of both copper-chromiumoxide and nickel gave faircolor and adequate hardening in thirty-two minutes. It will be noted aredisclosed as effective when the entire catalyst is added to the oilprior to hydrogenolysis. Accordingly, it will be obviousto one skilledin the art that if one of the components of the catalyst, that is thenickel, is added to the oil subsequent to the beginning ofhydrogenation, a proportionately higher amount of it may be used.

In such case the hydrogenating rate would be increased.

The temperatures under which my process may be carried out may be variedover a wide range. Temperatures of about 200 C. have been used withparticular success, although satisfactory resultsmay be obtained attemperatures of, for example, 130-250" C. At lower temperatures, thesynergistic effect described above is less marked and the reduction incolor and iodine value tends to be less. In general, lower temperaturesmay be employed when higher pressures are utilized. 'At more elevatedtemperatures, the oil has a tendency to decompose and there is formed anundesirable amount of unsaponifiable material. In'general, an increasein temperature will cause a proportionately greater color and iodinereduction.

It has been found desirable to limit the tim of operation to notmore'than substantially sixty minutes and, in some cases, toapproximately thirty minutes or less subsequent to the heating of theoil to a sufllcient temperature for effective decolorization andstabilization. Successful op.- erations'may be carried out, for example,in as little as ten to fifteen minues. I Although the re-- duction incolor and iodine value will be a function of the amount of time duringwhich the oil is maintained at elevated temperatures, it will be foundthat the maintenance of the oil at elevated temperatures may cause theformation of relatively large amounts of ketones, alcohols andhydrocarbons. For satisfactory use in good grade shortenings, forexample, it is desirable to reduce the iodine value of cottonseed oil toapproximately 70-75 as quickly as possible with the least amount ofunsaponifiable matter formed, and yet at the same time obtain the mostcomplete color removal possible.

In addition to the improved effect with respect to color particularlynoticeable in the case of cottonseed oil, it has been observed that thisprocess is particularly effective forstabilizing glyceride oils againstnormal oxidationand the development of rancidity. A glyceride oil whichhas been treated with hydrogen in the presence of a catalyst containingmetallic oxides and ac- I tive nickel in accordance with this invention,is

found to have a greater degree of stability than or saturation, or both,with a catalyst containing active nickel alone.

Furthermore, the present process is particularly effective forstabilizing glyceride oils such as soybean oil against reversion. whichhas been treated with hydrogen in accordance with this invention isfound to be stable against reversion to the characteristic objectionableodor and flavor which normally develop in soybean oil products producedin accordance with the prior art, particularly when the oil is subjectedto the elevated temperatures utilized in deep frying.

It is to be understood that a glyceride oil which has been hydrogenatedin accordance with the invention, in addition to having an improvedcolor and stability against reversion under deep frying conditions, willhave upon further treatment in the conventional manner, such as byfiltering, deodorizing, chilling, aerating, texturizing or otherwisefinishing, the qualities requisite for conversion to and use in anall-purpose shortening. A shortening made from oils treated inaccordance with this invention is plastic and workable over a reasonablerange of temperature and may be readily creamed and when used for bakingpurposes, produces'cakes of good vol- .andto illustrate the novelresults obtained. It

is to be understood that the process is applicable to the treatment ofall glyceride oils and fats or mixtures thereof of animal, vegetable ormarine origin which are susceptible to an improvement in color andstability. Among the oils which have been treated satisfactorily inaccordance an oil hardened to the same degree of plasticity with myinvention are, for example, palm oil, sesame oil, peanut oil, coconutoil and tallow.

The variations to which this invention is susceptible by one skilled inthe art are intended to be included within the scopev of the invention.

I claim:

1. A method of simultaneously decolorizing, stabilizing and hardeningglyceride oils, which comprises treating the oil at an elevatedtemperature'with hydrogen in the presence of a catalyst comprisingnicked and a metallic oxide of the general formula XY-O, in which Xrepresents at least one metal selected from the minor sub-groups ofgroups I and II, Y represents at least one metal selected from the minorsubgroups of groups V and VI of the periodic classification, and 0represents oxygen.

2. A method of simultaneously decolorizing, stabilizing and hardeningglyceride oils, which comprises treating the oil at an elevatedtemperature with hydrogen in the presence of a catalyst comprisingnickel and a metallic oxide of the general formula XY-O in which X rep-1 resents at least one of the metals of the group consisting of copperand silver, Y represents at least one of the metals of the groupconsisting of chromium, vanadium, tungsten and uranium, and 0 representsoxygen.

3. A method of. simultaneously decolorizing, stabilizing and hardeningglyceride oils which comprises treating the oil at'anelevatedtemperature with hydrogen in the presence of a catalystcomprising nickel and copper-chromiumoxide.

4. A method ofsimultaneously decolorizing, stabilizing and hardeningglyceride oils, which A soybean oilv comprises treating'the oil at anelevated temperature with hydrogen in the presence of a catalystcomprising nickel and silver-chromiumoxide. e

5. A method of simultaneously decolorizing, stabilizing and hardeningglyceride oils, which .comprises treating the oil at an elevatedtemperature with hydrogen in the presence of .a catalyst comprisingnickel and copper-vanadiumoxide. v

6.-A method of simultaneously decolorizing, stabilizing and hardeningglyceride oils, which comprises treatingthe oil at an elevatedtemperatur with hydrogen in the presence of a catalyst comprising nickeland a metallic oxide of the general formula XY- in which X represents atleast one of the metals of the group consisting of copper and silver, Yrepresents at least one of the metals of the group consisting ofchromium, vanadium, tungsten and uranium, and 0 represents oxygen, saidcatalyst being stabilized by the presence of an oxide of an alkalineearth metal.

'7. A method of simultaneously decolorizing,,

' proportion of one atom of X to one atom of Y to one tenth mole ofalkaline earth metal.

8. A method of simultaneously decolorizing, stabilizing and hardeningglyceride oils which comprises treating the oil at an elevatedtemperature with hydrogen in the presence of a catalyst comprisingnickel and a metallic oxide of the general formula X--Y -O in which Xrepresents at least one of the metals of the group consisting of copperand silver, Y represents at least one of the metals of the groupconsisting of chromium, vanadium, tungsten and uranium,

mium,vanadium, tungsten and uranium, and 0 represents oxygen, saidnickel being present in amount not more than substantially 0.1% and saidmetallic oxides being present in amount not less than substantially0.1%, based on the Weight of th oil.

11. A method of simultaneously decolorizing,

amount of substantially 0.001 to 0.01% nickel and 0.2% metallic oxide,based on the weight of the oil.

12. A method of simultaneously decolorizing, stabilizing and hardeningglyceride oils, which comprises treating the oil at an elevatedtemperand 0 represents oxygen, said metals represented by X and Y beingpresent in substantially equal atomic proportions, said nickel beingpresent in amount not more than substantially 0.1% and said metallicoxides being present in amount not less than substantially 0.1%, basedon the weight of the oil.

9. A method of simultaneously, decolorizing, stabilizing and hardeningglyceride oils, which comprises treating the oil at an elevatedtemperature with hydrogen in the presence of a catalyst comprisingnickel and a major proportion of a metallic oxide of the general formulaXYO in which X represents at least one of the metals of the groupconsisting of copper and silver, Y

ature under a pressure of not less than substantially 100 atmosphereswith hydrogen in the presence of a catalyst comprising nickel and ametallic oxide of the general formula X--YO in which X represents atleast one of the metals of the group consisting of copper and silver, Yrepresents at least one of the metals of the group consisting ofchromium, vanadium, tungsten, and uranium, and 0 represents oxygen, saidcatalyst being present in amount of substantially 0.001% to, 0.01%nickel and 0.2% metallic oxide, based on the weight of the oil.

13. A method of simultaneously decolorizing, stabilizing and hardeningglyceride oils, which comprises maintaining the oil at a temperature ofnot more than 250 C. while treating the oil with hydrogen gas and in thepresence of a catalyst comprising nickel and a metallic oxide 01' thegeneral formula XYO in which X represents at least one of the metals ofthe group consisting of copper and silver, Y represents at least one ofthe metals of the group consisting of chromium, vanadium, tungsten, anduranium, and 0 represents oxygen.

14. A method of simultaneously decolorizing, stabilizing and hardeningglyceride oils, which comprises maintaining the oil at a temperature ofnot more than substantially 250 C."'while treating the oil with hydrogenunder a pressure of not less than substantially 100 atmospheres and inthe presence of a catalyst comprising nickel and a metallic oxideselected from the group consisting of metallic oxides of the generalformula XYO inwhich X represents at least one of the metals of the groupconsisting of copper and silver, Y represents at least one of the metalsof the group consisting of chromium, vanadium,

tungsten, and uranium, and 0 represents oxygen.

15. A method of simultaneously decolorizing,

stabilizing and hardening glyceride oils, which represents at least oneof the metals of the group at least one of the metals of the groupconsisting of copper and silver, Y represents at least one of th metalsof the group consistng of chrocomprises maintaining the oil at atemperature of not more than substantially 240 C. for a period of timeof not less than substantially ten minutes while treating with hydrogenin the presence of a catalyst comprising nickel and a catalyst selectedvfrom the group consisting of metallic oxides of the general formula XY-Oin which X represents at least one of the metals of the group consistingof copper and silver, Y represents at least one of the metals of thegroup consisting of chromium, Vanadium, tungsten, and uranium, and 0represents oxygen.

16. A method of simultaneously decolorizing, stabilizing and hardeningghrceride oils. which comprises maintaining the oil at a temperature ofnot more than substantially 250 C. while treating with hydrogen in thepresence of a catalyst comprising nickel and a catalyst selected fromthe group consisting of metallic oxides of the general formula X-Y-O inwhich X represents at least one of the metals of the group consisting ofcoppar and silver, Y represents at least one oi the metals of the groupconsisting. of chromium, vanadium, tungsten, and uranium, and Orepresents oxygen, said nickel being present in amount lected from thegroup consisting of nickel, cobalt.

platinum and palladium and a metallic oxide of the general formulaX-Y-O, in which X represents at least one metal selected from the minorsub-groups of Groups I and II, Y represents atleast one metal selectedfrom the minor sub groups of Groups V and VI of the PeriodicClassifications, and 0 represents oxygen.

'18. A method of simultaneously decolorizing, stabilizing and hardeningglyceride oils, which comprises treating the oil at an elevatedtemperature with hydrogen in the presence of a catalyst comprising acatalytically active metal selected from the group consisting of nickel,cobalt, platinum and palladium and a metallic oxide of the generalformula XYO in which X represents at least one or the metals of thegroup consisting of copper and silver. Y represents at least one of themetals oi the group consisting of chromium, vanadium, tungsten anduranium, and 0 represents oxygen.

19. A method of simultaneously decolorizing, stabilizing and hardeningglyceride oils, which comprises treating the oii at an elevatedtemperature with hydrogen in the presence of a catalyst comprising acatalytically active metal selected from the group consisting of nickel,cobalt, platinum and palladium and a metallic oxide of the generalformula X-Y-O in which X represents at least one of the metals of thegroup consisting of copper and silver, Y represents at least one of themetals or the group consisting of chromium,

vanadium, tungsten and uranium, and O represents oxygen, said catalystbeing stabilized by the presence of an oxide of an alkaline earth metal.

' WILLIAM J; PATERSON.

1 CERTIFICATE OF coRR cmN-.- v

I Sep m 5. 9 m- WILLIAM J. 'PAmRsQN.

' It is hereby certified that error appears in the printed Specificationof the above humberegl pateht I-equ:! 1:'1ng correctionas follows: Page5, sec-- 0nd column, lirle, 50, 61-9111; 1, fof Ynieked" read --niEke1page 6, second eolumn, line 611., cl aim 15, "for "214.0 C." read +25 OC.--; and that the said Letters Patent ehould'be read with thiscor'rectien therein that the me m w 'coriform. t6- the recerdof the casein the Patent Office.

4 Signed and seaIeQ-thisfilst day ef October, .A; D. 191m" I LeslieFrazer (Seal) Actihg' Cpmnissioner of Patents.

